Method for linking two or more metals for photo and electronic materials

ABSTRACT

Embodiments of the invention are directed to bimetallic substituted triazole compounds and methods to prepare the compounds. The compounds include at least one 1,2,3-triazole that is substituted by two metal ions in the 1 and 4 or 5 position of the triazole ring. An iClick reaction between a metal acetylide and a metal azide results in the bimetallic substituted triazole ring. Depending on the metal acetylide and a metal azide used monomeric bimetallic substituted triazole compounds, oligomeric bimetallic triazole compounds, or polymeric bimetallic triazole compounds are formed. Polymeric bimetallic triazole compounds can be linear, branched, ladder, two-dimensional network, or three-dimensional networks.

This application is a continuation-in-part of International PatentApplication No. PCT/US2011/057851, filed Oct. 26, 2011, which claims thebenefit of U.S. Provisional Patent Application Ser. No. 61/407,248,filed Oct. 27, 2010, the disclosures of which are hereby incorporated byreference in their entirety.

BACKGROUND OF INVENTION

A Click reaction is one that yields a product quantitatively or nearlyso while being tolerant to a wide range of solvents, including water,and pH conditions and having a strong thermodynamic driving force. Thesecharacteristics are attractive when designing new approaches to buildingsmall molecules and materials. Reactions that have the characteristicsof a Click reaction were originally pursued in the field of drugdiscovery, and the approach has led to an immense number of potentialdrug targets in a manner that is easier and less expensive than earliersynthetic approaches used for drug discovery.

Of the reactions that are classified as Click reactions, the mostrecognized and prolifically applied is the copper catalyzed azide-alkynecycloaddition (CuAAC) to yield 1,4-disubstituted 1,2,3-triazoles, asshown in Scheme 1, below. This reaction is particularly accessible dueto: the ease of synthesis of the alkyne and azide functional reactantsin nearly quantitative yields; the tolerance of the reaction to a widevariety of solvents, including water; the regioselectivity of thereaction toward synthesis of 1,4-disubstituted triazoles; and the hightolerance of alkyne and azide functional groups to most other functionalgroups. CuAAC represents the qualities of a Click reaction so well thatit is often referred to simply as “the click reaction”.

Despite the great activity of Click Chemistry and, particularly, CuAAC,there are few applications of these reactions in inorganic ororganometallic chemistry. CuAAC has been applied to thefunctionalization metal clusters with organic moieties and to thesynthesis of organic ligands to be employed with metal ions. Neither theCuAAC nor any Huisgen 1,3-dipolar cycloaddition reaction has not beenexplored to directly link two or more metal ions. Organobimetallic andmultimetallic compounds employing the cycloaddition of metal-azides andmetal-acetylides should be useful as bimetallic catalysts, polymers, and2- or 3-dimensional covalent metal organic networks, including thosewhere a plurality of identical or different metals are isolated and atleast two metals are separated by a 1,2,3-triazole ring.

BRIEF SUMMARY

Embodiments of the invention are directed to bimetallic substitutedtriazole compounds comprising one or more 1,2,3-triazole units where atleast one of the triazole units is substituted by two metal ions in the1 and 4 or 5 positions. The triazole units can be further substitutedwith an organic substituent in the 4 or the 5 position that is notsubstituted by the metal ion. The metal ions can be Au, Ni, Pd, Pt, Ru,Fe, Mn, Rh, Ir, Cr, Cu,W or any other group 3-16 metal. The compound caninclude at least one ligand attached to at least one metal ion, wherethe ligand can be, for example, a phosphorous based ligand, nitrogenbased ligand, cyclopentadienyl derivative, carbon monoxide, nitrosyl,alkyl, aryl, or pincer-type ligand that can be neutral or charged andmonodentate, bidentate, polydentate and bridging or chelating. In someembodiments of the invention, a plurality of triazole units is presentwith at least one metal attached to two triazole units. In otherembodiments of the invention a multiplicity of triazole units areconnected by a multiplicity of metal ions as a linear polymeric chain ora polymeric network. According to an embodiment of the invention,metal-clusters with one or more azide and/or one or more acetylidegroups can be used. The use of metal comprising compounds incycloaddition reactions, incorporates an inorganic component to theprocess and products. Hence, the reaction is an “inorganic click” or“iClick” reaction. According to embodiments of the invention, the iClicreaction can proceed uncatalyzed, as in Huisgen 1,3-dipolarcycloadditions, or can proceed in the presence pf a copper(I) catalyt.

Other embodiments of the invention are directed to a method for thepreparation of the bimetallic substituted triazole compounds where atleast one metal acetylide and at least one metal azide are combined andundergo cycloaddition to form a triazole ring. The metal azide can be ametal with 1 to 6 azide groups and the metal acetylide can be a metalwith 1 to 6 acetylide groups, which can be unsubstituted or substitutedwith an organic group.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows the molecular structure of homobimetallic triazole complex3_(1,5), according to an embodiment of the invention, as determined bysingle crystal X-ray diffraction experiments.

FIG. 2 shows a ¹H NMR spectrum of a mixture of 3_(1,5) and 3_(1,4)according to an embodiment of the invention in CDCl₃.

FIG. 3 shows a ³¹P{¹H} NMR spectrum of a mixture of 3_(1,5) and 3_(1,4),according to an embodiment of the invention referenced to PPh₃ as anexternal standard.

FIG. 4 shows a ¹³C{¹H} NMR spectrum of a mixture of 3_(1,5) and 3_(1,4)according to an embodiment of the invention.

FIG. 5 shows a ³¹P{¹H} NMR spectrum of a mixture of 3_(1,5) and 3_(1,4)at −40° C. according to an embodiment of the invention.

FIG. 6 shows a FT-IR spectrum of a mixture of 3_(1,5) and 3_(1,4),according to an embodiment of the invention.

FIG. 7 shows the molecular structure of complex of cis-6-Ph, accordingto an embodiment of the invention, as determined by single crystal X-raydiffraction experiments.

FIG. 8 shows the molecular structure of complex of cis-6-Et, accordingto an embodiment of the invention, as determined by single crystal X-raydiffraction experiments.

FIG. 9 shows the molecular structure of complex of 7, according to anembodiment of the invention, as determined by single crystal X-raydiffraction experiments.

FIG. 10 shows the molecular structure of complex of cis-11, according toan embodiment of the invention, as determined by single crystal X-raydiffraction experiments.

FIG. 11 shows the molecular structure of complex of 3-NO₂, according toan embodiment of the invention, as determined by single crystal X-raydiffraction experiments.

DETAILED DISCLOSURE

Embodiments of the invention are directed to a method, an iClickreaction, where 1,3-dipolar cycloaddition is employed to link two ormore metal ions upon combining a metal-coordinated azide complex and ametal-coordinated alkyne complex with the formation of a 1,4-bimetallicsubstituted 1,2,3-triazole, as shown in Scheme 2, below, for reactionbetween a metallic monoacetylide and a metallic monoazide where M and M′represent metal centers that can be the same metal or different metals,L is independently any ligand, and R is hydrogen or any organicsubstituent. In other embodiments of the invention, the cycloadditioncan result in a 1,5-bimetallic substituted triazole, as shown in Scheme3, or a combination of 1,4- and 1,5-bimetallic substituted triazole. Theselectivity towards 1,4- or 1,5-addition depends upon the metal ion orions and other substituents on the acetylide and whether the reactionemploys copper(I) as a catalyst. In embodiments of the invention, one orboth of M and M′, the metal centers, are not a single metal ion, rather,M and/or M′ is a cluster complex where a plurality of one metal ion or aplurality of two or more metal ions reside as a cluster. In theseembodiments of the invention, one or more metal ions of the cluster arebonded to at least one azide or to at least one acetylide. Althoughother ligands need not be present, the cluster can have one or moreligands, such as, but not limited to, carbon monoxide, halides,isocyanides, alkenes, or hydrides, included to stabilize the clustercomplex.

Embodiments of the invention are directed to bimetallic complexes,trimetallic complexes, one-dimensional metallopolymers andmetallooligomers, two-dimensional metal-organic networks, andthree-dimensional metallo-networks formed from azide and acetylidereagents. Each of these products, according to embodiments of theinvention, can vary by the number and identity of the combined metalions, ligands, regioselectivity of the addition product, coordinationgeometries, oxidation states, and redox combinations that permit theseorganometallic species to be used in a variety of applications.Currently, methods for linking two metal ions are limited, and linkingtwo or more metal ions in a controllable fashion is difficult. TheiClick reaction has a strong thermodynamic driving force thateffectively couples nearly any metal azide and any metal acetyliderapidly and displays a quantitative or nearly quantitative efficiency.The iClick reaction can be catalyzed. For example, a catalytic amount ofcopper (I) salt can be added to the reaction mixture, or formed in thereaction mixture by the addition of a copper (II) salt and copper metalor other reducing agent.

For bimetallic triazoles, as illustrated in Schemes 2 and 3, the metalions, M and M′ are independently a metal from groups 3-12 or a maingroup metal from groups 13-16. For example, the metal ions can be Au,Ni, Pd, Pt, Ru, Fe, Mn, Rh, Ir, Cr, Cu, and/or W ions. Ligands can beneutral or charged and can be monodentate, bidentate or polydentate andchelating a single metal or bridging a plurality of metals. Commonligands include but are not limited to: phosphorous based ligands;nitrogen based ligands, including pyridine, bipyridine, and terpyridine;cyclopentadienyl derivatives; carbon monoxide; nitrosyl; alkyl; aryl;and pincer-type ligands. In some embodiments of the invention, theligand can include functional groups to permit their association orbonding to a surface, incorporation into a resin, or polymerization tomaterials with fixed bimetallic triazole units for use as heterogeneouscatalysts.

In these bimetallic triazoles, the R group can be H, C₁-C₃₀ alkyl,C₆-C₂₂ aryl, C₇-C₃₀ alkylaryl, C₇-C₃₀ arylalkyl, C₂-C₂₉ heteroaryl,C₃-C₃₀ alkylheteroaryl, C₃-C₃₀ heteroarylalkyl, C₂-C₃₀ alkenyl, C₈-C₃₀alkenylaryl, C₈-C₃₀ arylalkenyl, C₄-C₃₀ alkenyiheteroaryl, or C₄-C₃₀heteroarylalkenyl and can be attached at any possible carbon of the Rgroup to the triple bond of the reagent acetylide and the C—C doublebond of the product triazole. Alkyl groups can be linear, branched,multiply branched, cyclic, polycyclic, or any combination thereof. Arylgroups can be phenyl, fused ring, for example, a naphthyl group, ormulti-ring, for example, biphenyl groups, with any geometry orsubstitution pattern. Alkylaryl groups are those connected to the triplebond of the reagent acetylide at any carbon of an aryl ring, which issubstituted with one or more alkyl groups, where an alkyl portion can bean alkylene chain disposed between two aryl portions. Arylalkyl groupsare those connected to the triple bond of the reagent at any carbon ofthe alkyl portion and have one or more aryl groups attached at anycarbon of the alkyl portion or inserted within the alkyl portion of thegroup. Heteroaryl groups contain one or more five-membered or largeraromatic heterocyclic rings where one or more heteroatoms, for example,O, N, or S, are included in the aromatic ring and can be a single ring,fused rings, or multi-ring, where one or more ring of the fused ormulti-ring group has one or more heteroatoms. Alkenyl groups can haveone or more double bonds situated anywhere in the group where multipledouble bonds can be isolated, conjugated, or a mixture of isolated andconjugated double bonds and where the alkenyl group can be a vinyl groupor an internal double bond with any E or Z in geometry or anycombination of vinyl with E or Z geometry for multiple double bonds. AnyR groups can be substituted at any position with, for example, nitro,hydroxy, C₁-C₃₀ alkoxy, C₆-C₁₄ aryloxy, C₇-C₃₀ arylalkyloxy, C₂-C₃₀alkenyloxy, C₂-C₃₀ alkynyloxy, C₈-C₃₀ arylalkenyloxy, C₈-C₃₀arylalkynyloxy, CO₂H, C₂-C₃₀ alkylester, C₇-C₁₅ arylester, C₈-C₃₀alkylarylester, C₃-C₃₀ alkenylester, C₃-C₃₀ alkynylester, NH₂, C₁-C₃₀alkylamino, C₆-C₁₄ arylamino, C₇-C₃₀ (arylalkyl)amino, C₂-C₃₀alkenylamino, C₂-C₃₀ alkynylamino, C₈-C₃₀ (arylalkenyl)amino, C₈-C₃₀(arylalkynyl)amino, C₂-C₃₀ dialkylamino, C₁₂-C₂₈ diarylamino, C₄-C₃₀dialkenylamino, C₄-C₃₀ dialkynylamino, C₇-C₃₀ aryl(alkyl)amino, C₇-C₃₀di(arylalkyl)amino, C₈-C₃₀ alkyl(arylalkyl)amino, C₁₅-C₃₀aryl(arylalkyl)amino, C₈-C₃₀ alkenyl(aryl)amino, C₈-C₃₀alkynyl(aryl)amino C(O)NH₂ (amido), C₂-C₃₀ alkylamido, C₇-C₁₄ arylamido,C₈-C₃₀ (arylalkyl)amido, C₂-C₃₀ dialkylamido, C₁₂-C₂₈ diarylamido,C₈-C₃₀ aryl(alkyl)amido, C₁₅-C₃₀ di(arylalkyl)amido, C₉-C₃₀alkyl(arylalkyl)amido, C₁₆-C₃₀ aryl(arylalkyl)amido, thiol, C₁-C₃₀hydroxyalkyl, C₆-C₁₄ hydroxyaryl, C₇-C₃₀ hydroxyarylalkyl, C₃-C₃₀hydroxyalkenyl, C₃-C₃₀ hydroxyalkynyl, C₈-C₃₀ hydroxyarylalkenyl, C₈-C₃₀hydroxyarylalkynyl, C₃-C₃₀ polyether, C₃-C₃₀ polyetherester, C₃-C₃₀polyester C₃-C₃₀ polyamino, C₃-C₃₀ polyaminoamido, C₃-C₃₀polyaminoether, C₃-C₃₀ polyaminoester, C₃-C₃₀ polyamidoesterC₃-C₃₀alkylsulfonic acid, C₃-C₃₀alkylsulfonate salt, C₁-C₃₀ carboxylatesalt, thiocarboxylate salt, dithiocarboxylate salt or C₃-C₃₀alkylC₁-C₄trialkyammonium salt. Asymmetric functional groups, such as ester andamido, can have either orientation with respect to their orientationrelative to the triazole ring. Heteroatoms in substituents can be at anyposition of those substituents, for example, oxygen of an ether or esteror nitrogen of an amine or amide can be in the alpha, beta, gamma or anyother position relative to the point of attachment to the base portionof the R group. Heteroatom containing substituents can have a pluralityof heteroatoms; for example, ether can be a monoether, a diether or apolyether, amine can be a monoamine, a diamine or a polyamine, ester canbe a monoester, a diester, or a polyester, and amide can be a monoamide,a diamide or a polyamide. Ethers and esters groups can be thioethers,thioesters and hydroxy groups can be thiol (mercapto) groups, wheresulfur is substituted for oxygen. Salts can be those of alkali or alkaliearth metals, ammonium salts, or phosphonium salts.

In an embodiment of the invention, linear metallopolymers can be formedby the addition of trans-diazide octahedral complexes withtrans-diacetylide octahedral complexes, as shown below in Scheme 4.Inclusion or substitution of other geometries, for example, cis-diazideand cis-diacetylide octahedral complexes, or disubstituted tetrahedralcomplexes, allows for the preparation of cyclic or macrocyclicmetallopolymers. These metallopolymers can display extended electrondelocalization through multiple metal centers linked by triazole rings.Such conjugated polymers can be used in applications that exploit theirnon-linear optical properties, such as optical signal processing,switching, and frequency generation in optical data storage, opticalcommunication, and optical image generation devices. Variation in thetriazole structure allows control of the effective m conjugation lengthin these polymers, which determines the polymer's optical gap. Thestructure of R is as for the bimetallic triazoles described above. As aplurality of metallic diacetylide and metallic diazide can be used, aplurality of different Ms and/or M's can be included in a singlepolymer. The metals can be any selected from group 3-12 metals and maingroup metals from groups 13-16. For example, the metals can be Au, Ni,Pd, Pt, Ru, Fe, Mn, Rh, Ir, Cr, Cu, and/or W. A plurality of different Rgroups can be used, where a single metallic diacetylide has twodifferent R groups, an asymmetric metallic diacetylide, or when two ormore different metallic diacetylides are used where the diacetylides aresymmetric, asymmetric, or any combination thereof. Polymers withdifferent degrees of polymerization can be formed by varying the ratioof the metallic diacetalide and metallic diazide reagents, for example,a ratio of n/n+1 or n+1/n to yield azide end-groups or acetalideend-groups, respectively. The linear metallopolymer, which can beconsidered a linear metallooligomer, is formed when n/n+1 is relativelysmall, for example, when n/n+1 is about 9/9+1 or less. Themetallooligomers can be cyclic oligomers or a mixture of linear andcyclic metallooligomers.

In another embodiment of the invention, one or more metallicmonoacetylides and/or metallic monoazides are included with the metallicdiacetylides and metallic diazides to control the degree ofpolymerization of the metallopolymers. In one embodiment of theinvention, when one or more metallic monoacetylides are employed, aportion of the R groups can have functionality appropriate for use ofthe metallopolymers or metallooligomers as macromers for a secondpolymerization. The functional R groups can be only on metallicmonoacetylides or they can be included in a portion of the metallicdiacetylides. For example, a vinyl group, such as an acrylate,methacrylate, or styrene group can be included in the metallicmonoacetylides, or a cyclic ether, for example, an epoxide, can beincluded for an addition chain growth polymerization of the macromer, orits copolymerization with a second monomer with like or copolymerizablegroup for crosslinking the metallopolymer or inclusion of themetallopolymer, into a resin at a small quantity. In another embodimentof the invention, the R groups of a portion of the metallicmonoacetylides can include functionality that allows the linearmetallopolymers or linear metallooligomers to be used as a macromer by acondensation or addition step growth polymerization with a complementarymonomer. Alternatively an organic diacetylide and/or an organic diazidecan be included into the iClick reaction mixture with the metallicdiacetylides and metallic diazides to decouple the effective πconjugation length from the degree of polymerization of the polymer,where the proportion of metallic diacetylides and metallic diazides toall diacetylides and diazides defines the conjugation length while theproportions of all diazides to all diacetylides define the molecularweight of the linear polymer. By inclusion of metallic or organic tri-,tetra-, penta-, or hexaacetylides and/or metallic or organic tri-,tetra-, penta-, or hexatriazides into the mixture of diazides anddiacetylides, networks can be formed.

In another embodiment of the invention the iClick reaction between:metal tetraazides and metal tetraacetylides; metal tetraazides and metaldiacetylides; metal diazides and metal tetraacetylides; metal triazidesand metal triacetylides; metal triazides and metal diacetylides; ormetal diazides and metal triacetylides results in the formation of atwo-dimensional network when the R groups are small; for example,hydrogen or methyl as the acetylide and azides are coplanar with themetal ions. Ladder polymer can result in some embodiments of theinvention where metal triacetylides and/or metal triazides are included.Scheme 5, below, illustrates the formation of a two-dimensional networkusing reaction between square planar metal centers where ligands areomitted for clarity in the illustrated product. The 1,4-substitutedtrizole linkages occurs in the presence of a copper(I) catalyst.

In some embodiments of the invention, 2-dimensional networks can besynthesized by reaction of mixtures of metal complexes that includecis-, trans-, and/or mer-acetylide or azido complexes, with or withoutincluded square planar metal complexes, where the 2-dimensional networksare of finite proportions and are effectively nanoparticle sized sheetsor flakes rather than the extended sheets that can be considered larger“bulk” materials. Such nanoparticulate two-dimensional networks can beemployed as heterogeneous catalysts, as-synthesized compound or afterpost-synthesis modification, such as after metal ion doping orcontrolled oxidation, or as photo-induced catalysts where the network isgenerated with hetero-metal centers with photochemistry tuned by theligands, for example, bipyridines or terpyridines, on the metal center.Use of trans-diacetylides or azides employed with square planartetraacetylides or tetraazides in a complementary manner can result in“bulk” two-dimensional networks. These “bulk” two-dimensional networksshare some features with metal organic frameworks (MOFs), such that theycan be used as heterogeneous catalysts or as surfaces for gas storage.Thin films of the two-dimensional polymers can be grown or spin-coatedafter synthesis onto electrode surfaces for use as electrocatalysts forredox reactions due to simultaneous conductivity and catalytic activity.The two-dimensional iClick formed materials are advantageous over MOFsdue to: the presence of strong covalent metal-carbon and metal-nitrogenbonds rather than the dative interactions of MOFs; surfaces wheredifferent metal ions residing in specific coordination environmentsrather than MOFs which inherently lack site specificity; mononuclearmetal nodes having strict geometric constraints due to the geometryimposed by the reactant acetylide and azide complexes; and the orderimposed by a 2-dimensional network from iClick reactions that occur atambient temperatures rather than those for MOFs where synthesis istypically carried out under hydrothermal conditions at elevatedtemperatures.

In another embodiment of the invention, three-dimensional networks areformed via copper(I) catalysis, where either homoleptic azides oracetylides, in octahedral or tetrahedral geometries, are paired withtheir complementary trans-diacetylide or diazide, as shown in Schemes 6and 7, below. Scheme 6 illustrates a network from a hexaacetylide and adiazide, where ligands are not shown in the network for easier view,that has a cubic cell. Scheme 7 shows only the reagent mixture, but doesnot show the diamond-like cell of the resulting network imposed by thetetrahedral geometry of one of the reagents. These materials have somesimilar properties as those for zeolitic imidazolate frameworks (ZIFs),which include high porosity and stability. Three-dimensional networksfrom iClick reactions are readily directed toward a specific utilitythrough the choice of substituent on the acetylide ligand(s) and bymodification of the two N-donor coordination sites that are available inthe three-dimensional network. The three-dimensional networks can beconstructed for use as gas storage/separation network, size-selectiveheterogeneous catalysts, or lithium ion battery separators.

METHODS AND MATERIALS General Methods

Glassware was oven dried before use. Unless otherwise specified, allmanipulations were performed under an inert atmosphere using standardSchlenk or glove-box techniques. Pentane, toluene, methylene chloride,and diethyl ether (Et₂O) were degassed by sparging with high purityargon and dried using a Glass Contours drying column. Methanol was driedover anhydrous copper(II)sulfate, distilled and stored over 4 Åmolecular sieves. Benzene-d₆ and chloroform-d₁ (Cambridge Isotopes) weredried over sodium-benzophenone ketyl and distilled or vacuum transferredand stored over 4 Å molecular sieves. Commercially available PPh₃AuCland TMSN₃ were used without further purification. Commercially availablephenylacetylene was distilled before use. The following materials werepurchased and used as received: chloro(dimethylsulfide)gold(I)(Sigma-Aldrich); chloro(triethylphosphine)gold(I) (Sigma-Aldrich);triphenylphosphine (Acros);cis-dichlorobis(triethylphosphine)platinum(II) (Sigma-Aldrich);potassium tetrachloroplatinate(II) (Aldrich), 1-ethynyl-4-nitrobenzene(Sigma-Aldrich); 1,1-bis(diphenylphosphino)methane (dppm)(Sigma-Aldrich); sodium azide (Acros). Ph₃PAuCCPh, Ph₃PAuN₃,PPh₃Au—C≡CPh, cis-(PPh₃)₂PtCl₂, cis-(PPh₃)₂Pt(N₃)₂ (4-Ph), PPh₃Au—Cl,PPh₃Au¹C≡CC₆H₄NO₂ (5-Ph), cis-(PEt₃)₂Pt(N₃)₂ (4-Et), and PEt₃Au¹N₃ (9),[Au(μ-dppm)Cl]₂ were prepared according to literature procedures. NMRspectra were obtained on Varian Mercury Broad Band 300 MHz, VarianMercury 300 MHz, or on Varian Inova 500 MHz spectrometers. Chemicalshifts are reported in δ (ppm). For ¹H and ¹³C {¹H} NMR spectra, thesolvent resonance was referenced as an internal reference, and for ³¹P{¹H} NMR spectrum, the 85% H₃PO₄ resonance was referenced as an externalstandard. Elemental analyses were performed at Complete AnalysisLaboratory Inc., Parsippany, N.J. FT-IR spectra were recorded on aThermo scientific instrument.

Synthesis of a Homo-Bimetallic Complex

As shown in Scheme 8, below, a sealable NMR tube was charged with 2 (10mg, 0.018 mmol), 1 (9 mg, 0.018 mmol), and benzene-d₆ (0.6 mL). After 24hours clear colorless crystals deposit. Crystals were collected andwashed with pentane to give the major product 3_(1,5) and <3% minorproduct 3_(1,4) (17 mg, 89% yield). 3_((1,5)): FIG. 1 shows themolecular structure of 3_(1,5) from single crystal X-ray diffraction.Tables 1 through 4, below, give crystal structure data for 3_(1,5) andTables 5 and 6, below, give computationally determined geometries for3_(1,5) and 3_(1,4). Additional support for the identification ofcomplex 3_(1,5) comes from NMR spectroscopy. FIG. 2 is a ¹H NMR spectrumof 3_(1,5) and 3_(1,4) in CDCl₃, FIG. 3 is a ³¹P{¹H} NMR spectrum of3_(1,5) and 3_(1,4), and FIG. 4 is a ¹³C{¹H} NMR spectrum of 3_(1,5) and3_(1,4). Two resonances appear in the ³¹P NMR spectrum at 43.93 and31.45 ppm for the two distinct phosphorous nuclei on complex 3_(1,5).Cooling the solution to −40° C. reveals two addition P resonancesattributable to 3_(1,4) (FIG. 5). FIG. 6 is an IR spectrum of 3_(1,5)and 3_(1,4) mixture. ¹H NMR (300 MHz, CDCl₃), δ (ppm): 8.43 (d, J=9 Hz),7.1-7.6 (m, aromatic). ³¹P{¹H} NMR (121.16 MHz, CDCl₃, 25° C.), δ (ppm):43.93 (bs, P AuC), 31.45 (bs, P AuN). ¹³C{¹H} NMR (75 MHz, CDCl₃), δ(ppm): 136.6 (s, C_(aromatic), triazolate), 134.2 (d, J_(PC)=14 Hz, o-C,overlapping, C—Au—P(C₆H₅)₃ and N—Au—P(C₆H₅)₃, 131.5 (bs, i-C,overlapping, C—Au—P(C₆H₅)₃ and N—Au—P(C₆H₅)₃, 129.1 (d, J_(PC)=11 Hz,m-C and p-C, overlapping, C—Au—P(C₆H₅)₃ and N—Au—P(C₆H₅)₃, 127.9 (s,C_(aromatic), triazolate), 126.4 (s, C_(aromatic), triazolate), 125.4(s, C_(aromatic), triazolate). 3_((1,4)): ¹H NMR (300 MHz, CDCl₃), δ(ppm): 8.6 (d, J=9 Hz), aromatic resoances overlapping with 3_((1,5))between 7.1-7.6. ³¹P{¹H} NMR (121.16 MHz, CDCl₃, −40° C.), δ (ppm):43.93 (s, P AuC), 31.45 (s, P AuN). Anal. Calcd. for C₄₄H₃₅N₃P₂Au₂: C,49.78; H, 3.32; N, 3.96. Found: C, 49.86; H, 3.41; N, 3.88.

TABLE 1 Atomic coordinates (× 10⁴) and equivalent isotropic displacementparameters (Å² × 10³) for 3_(1,5). U(eq) is defined as one third of thetrace of the orthogonalized Uij tensor. Atom x y z U(eq) Au1  8914(1)5890(1) 3253(1) 19(1) Au2  8468(1) 5595(1) 4198(1) 21(1) P1  8059(1)6682(1) 2920(1) 19(1) P2  7329(1) 6217(1) 4476(1) 27(1) N1  9633(2)5158(2) 3574(1) 20(1) N2 10267(2) 4683(2) 3452(1) 28(1) N3 10514(2)4236(2) 3737(1) 28(1) C1  9453(3) 5018(2) 3941(1) 18(1) C2 10022(3)4430(3) 4039(1) 21(1) C3 10111(3) 4014(3) 4390(1) 25(1) C4  9562(7)4050(8) 4675(3) 29(3) C5  9657(7) 3636(8) 5001(3) 34(3) C6 10293(7)3069(8) 5028(4) 25(3) C7 10815(9) 2945(7) 4711(4) 30(4) C8 10753(10)3388(9) 4404(4) 33(4) C4′  9782(6) 4390(7) 4735(3) 25(3) C5′  9847(6)4009(8) 5075(3) 32(3) C6′ 10228(7) 3316(8) 5104(4) 30(3) C7′ 10589(9)2975(7) 4803(4) 31(3) C8′ 10536(9) 3355(8) 4438(4) 29(4) C9  7056(3)5810(3) 4930(1) 27(1) C10  6202(3) 5729(3) 5055(2) 44(2) C11  6043(4)5396(4) 5400(2) 55(2) C12  6722(4) 5145(4) 5621(2) 51(2) C13  7564(3)5234(3) 5505(2) 38(1) C14  7729(3) 5565(3) 5157(1) 31(1) C15  7538(3)7231(2) 4558(1) 38(1) C16  7101(8) 7607(3) 4845(2) 49(3) C17  7308(12)8371(3) 4935(2) 61(4) C18  7952(10) 8760(3) 4738(2) 51(4) C19  8388(6)8385(4) 4451(4) 62(5) C20  8181(5) 7620(4) 4361(3) 41(5) C16′  7358(18)7658(9) 4912(6) 49(6) C17′  7669(19) 8424(9) 4966(4) 46(6) C18′ 8250(20) 8724(10) 4711(5) 60(6) C19′  8434(12) 8337(10) 4380(6) 51(8)C20′  8057(16) 7605(9) 4319(5) 42(8) C21  6341(3) 6148(3) 4206(2) 34(1)C22  5706(4) 6716(4) 4190(2) 61(2) C23  4951(4) 6592(5) 3991(2) 75(2)C24  4816(3) 5920(4) 3801(2) 57(2) C25  5428(3) 5343(4) 3812(2) 48(2)C26  6184(3) 5459(3) 4014(2) 42(1) C27  7690(3) 7506(3) 3190(1) 21(1)C28  6876(7) 7739(8) 3238(4) 35(3) C29  6655(7) 8402(8) 3454(4) 31(3)C30  7316(8) 8862(7) 3584(3) 21(3) C31  8153(9) 8664(7) 3518(3) 27(3)C32  8363(8) 8009(7) 3328(4) 26(3) C28′  6852(6) 7477(8) 3359(4) 23(3)C29′  6579(8) 8106(9) 3569(4) 34(4) C30′  7072(10) 8729(9) 3619(4) 37(4)C31′  7899(12) 8748(10) 3464(5) 46(5) C32′  8195(10) 8115(9) 3251(5)36(4) C33  8582(3) 7108(3) 2517(1) 19(1) C34  8365(3) 7843(3) 2378(1)24(1) C35  8780(3) 8130(3) 2065(1) 29(1) C36  9408(3) 7694(3) 1890(1)33(1) C37  9624(3) 6971(3) 2023(1) 31(1) C38  9219(3) 6676(3) 2338(1)25(1) C39  7120(3) 6174(3) 2733(1) 20(1) C40  6770(3) 6362(3) 2393(1)23(1) C41  6122(3) 5905(3) 2238(1) 30(1) C42  5813(3) 5265(3) 2423(1)29(1) C43  6139(3) 5086(3) 2771(2) 38(1) C44  6798(3) 5532(3) 2924(2)36(1) C45  4057(4) 3795(4) 2519(2) 57(2) C46  3524(4) 4396(4) 2590(2)58(2) C47  3201(4) 4522(3) 2931(2) 59(2) C48  3421(4) 4032(4) 3221(2)66(2) C49  3987(4) 3406(4) 3150(2) 58(2) C50  4295(3) 3310(4) 2801(2)52(2) C51  7654(5) 7447(4) 1222(3) 44(4) C52  7543(5) 6747(5) 1410(2)36(3) C53  6862(7) 6255(4) 1315(2) 42(3) C54  6291(6) 6464(5) 1032(2)40(4) C55  6402(5) 7165(6)  844(2) 45(3) C56  7083(5) 7656(4)  939(3)37(5) C51′  7545(5) 7313(6) 1200(3) 51(5) C52′  7268(6) 6586(6) 1321(3)57(4) C53′  6457(7) 6308(4) 1217(3) 40(3) C54′  5924(6) 6758(5)  991(2)34(3) C55′  6201(5) 7485(5)  869(2) 40(3) C56′  7012(6) 7762(4)  974(3)64(7)

TABLE 2 Bond lengths (in Å) for 3_(1,5). Bond Length Bond Length BondLength Au1-N1  2.032(3) C39-C44 1.392(6) C51′-C52′ 1.39(1) Au1-P12.2416(12) C40-C41 1.385(6) C51′-C56′ 1.39(1) Au2-C1  2.035(4) C41-C421.370(6) C52′-C53′ 1.39(1) Au2-P2 2.2846(12) C7′-C8′ 1.465(19) C53′-C54′1.39(1) P1-C27  1.807(5) C9-C14 1.386(7) C54′-C55′ 1.39(1) P1-C33 1.808(4) C9-C10 1.399(7) C55′-C56′ 1.39(1) P1-C39  1.819(4) C10-C111.384(8) P2-C15  1.796(4) C11-C12 1.381(8) P2-C21  1.810(5) C12-C131.373(7) P2-C9  1.820(5) C13-C14 1.394(7) N3-N2  1.332(5) C15-C20′1.337(18) N3-C2  1.365(5) C15-C16  1.39(1) N1-N2  1.346(5) C15-C20 1.39(1) N1-C1  1.368(5) C15-C16′  1.49(2) C1-C2  1.383(6) C16-C17 1.39(1) C2-C3  1.457(6) C17-C18  1.39(1) C3-C8′  1.319(14) C18-C19 1.39(1) C3-C4  1.327(11) C19-C20  1.39(1) C3-C8  1.463(16) C16′-C17′1.415(14) C3-C4′  1.486(11) C17′-C18′ 1.376(14) C4-C5  1.377(14)C18′-C19′ 1.393(15) C5-C6  1.385(16) C19′-C20′ 1.402(14) C6-C7 1.410(17) C21-C22 1.384(6) C7-C8 1.34(2) C21-C26 1.390(7) C4′-C5′ 1.387(13) C22-C23 1.382(7) C5′-C6′  1.330(15) C23-C24 1.357(8) C6′-C7′ 1.349(17) C24-C25 1.370(7) C27-C28′  1.429(12) C25-C26 1.387(7) C27-C32 1.439(13) C27-C32' 1.323(15) C28-C29  1.419(14) C27-C28 1.329(11)C29-C30  1.372(16) C42-C43 1.381(7) C30-C31  1.356(17) C43-C44 1.386(6)C31-C32  1.354(16) C45-C46 1.345(8) C28′-C29′  1.385(15) C45-C501.362(9) C29′-C30′  1.324(18) C46-C47 1.339(9) C30′-C31′  1.39(2)C47-C48 1.380(9) C31′-C32′  1.41(2) C48-C49 1.409(9) C33-C38  1.388(6)C49-C50 1.350(8) C33-C34  1.400(6) C51-C52  1.39(1) C34-C35  1.383(6)C51-C56  1.39(1) C35-C36  1.375(7) C52-C53  1.39(1) C36-C37  1.373(7)C53-C54  1.39(1) C37-C38  1.387(6) C54-C55  1.39(1) C39-C40  1.373(6)C55-C56  1.39(1)

TABLE 3 Bond angles (°) for 3_(1,5). Bond Angle Bond Angle Bond AngleN1-Au1-P1  176.9(1) C4-C3-C2 125.6(6) C22-C21-C26 117.3(5) C1-Au2-P2177.99(12) C8′-C3-C8  13.7(9) C22-C21-P2 124.8(5) C27-P1-C33  104.6(2)C4-C3-C8 116.1(9) C26-C21-P2 117.9(4) C27-P1-C39 108.80(19) C2-C3-C8117.0(7) C23-C22-C21 120.5(6) C33-P1-C39  104.8(2) C8′-C3-C4′ 115.8(8)C24-C23-C22 121.3(6) C27-P1-Au1 111.98(15) C4-C3-C4′  28.5(5)C23-C24-C25 119.7(6) C33-P1-Au1 114.18(14) C2-C3-C4′ 118.4(5)C24-C25-C26 119.4(6) C39-P1-Au1 111.97(15) C8-C3-C4′ 121.5(8)C25-C26-C21 121.8(5) C15-P2-C21  107.6(2) C3-C4-C5 124.1(9) C32′-C27-C28107.2(9) C15-P2-C9  105.5(2) C4-C5-C6 119.9(11) C32′-C27-C28′ 119.3(9)C21-P2-C9  105.0(2) C5-C6-C7 116.9(11) C39-C40-C41 120.4(4) C15-P2-Au2112.77(16) C8-C7-C6 122.4(13) C42-C41-C40 120.8(5) C21-P2-Au2 112.54(18)C7-C8-C3 119.5(13) C41-C42-C43 119.3(4) C9-P2-Au2 112.88(15) C5′-C4′-C3120.1(9) C42-C43-C44 120.2(5) N2-N3-C2  107.9(4) C6′-C5′-C4′ 121.5(11)C43-C44-C39 120.2(5) N2-N1-C1  110.7(3) C5′-C6′-C7' 120.6(12)C46-C45-C50 119.5(7) N2-N1-Au1  126.0(3) C6′-C7′-C8′ 120.0(12)C47-C46-C45 121.7(7) C1-N1-Au1  122.8(3) C3-C8'-C7′ 121.6(12)C46-C47-C48 119.9(6) N3-N2-N1  108.0(4) C14-C9-C10 119.1(5) C47-C48-C49118.8(6) N1-C1-C2  104.1(4) C14-C9-P2 117.9(4) C50-C49-C48 118.7(6)N1-C1-Au2  120.2(3) C10-C9-P2 123.0(4) C49-C50-C45 121.4(6) C2-C1-Au2 135.6(3) C11-C10-C9 119.7(5) C52-C51-C56 120.0(8) N3-C2-C1  109.3(4)C12-C11-C10 120.5(5) C27-C32′-C31′ 120.8(13) N3-C2-C3  121.0(4)C13-C12-C11 120.5(6) C38-C33-C34 119.2(4) C1-C2-C3  129.6(4) C12-C13-C14119.4(5) C38-C33-P1 117.9(3) C8′-C3-C4  105.0(8) C9-C14-C13 120.8(5)C34-C33-P1 122.9(3) C8′-C3-C2  125.4(7) C20′-C15-C16 122.9(8)C35-C34-C33 120.0(4) C20′-C15-C20 10.0(12) C28-C27-C28′  25.9(6)C36-C35-C34 120.2(5) C16-C15-C20  120.0(6) C32′-C27-C32  16.8(8)C37-C36-C35 120.4(5) C20′-C15-C16′  114.9(11) C28-C27-C32 117.0(8)C36-C37-C38 120.3(5) C16-C15-C16′ 18.4(9) C28′-C27-C32 121.8(7)C37-C38-C33 120.0(4) C20-C15-C16′  109.2(7) C32′-C27-P1 121.6(7)C40-C39-C44 119.0(4) C20′-C15-P2  117.9(8) C28-C27-P1 127.1(6)C40-C39-P1 121.9(3) C16-C15-P2  119.0(4) C28′-C27-P1 119.1(6) C44-C39-P1118.8(4) C20-C15-P2  120.7(4) C32-C27-P1 115.4(6) C53-C52-C51 120.0(7)C16′-C15-P2  125.7(7) C27-C28-C29 122.7(9) C52-C53-C54 120.0(8)C15-C16-C17  120.(7) C30-C29-C28 118.0(9) C53-C54-C55 120.0(8)C18-C17-C16  120.0(9) C31-C30-C29 120.1(10) C54-C55-C56 120.0(8)C19-C18-C17  120.0(9) C32-C31-C30 121.7(11) C55-C56-C51 120.1(8)C18-C19-C20  120.0(9) C31-C32-C27 120(1) C52′-C51′-C56′ 120.0(6)C19-C20-C15  120.0(8) C29′-C28′-C27 118.7(10) C51′-C52′-C53′ 120.0(6)C17′-C16′-C15  120.8(13) C30′-C29′-C28′ 122.0(12) C54′-C53′-C52′120.0(6) C18′-C17′-C16′  118.5(13) C29′-C30′-C31′ 119.4(14)C55′-C54′-C53′ 120.0(6) C17′-C18′-C19′  121.5(14) C30′-C31′-C32′119.7(14) C56′-C55′-C54′ 120.0(6) C18′-C19′-C20′  118.4(15)C15-C20′-C19′ 125.4(15) C55′-C56′-C51′ 120.0(6)

TABLE 4 Anisotropic displacement parameters (Å² × 10³) for 3_((1, 5)).The anisotropic displacement factor exponent takes the form: −2π²[h²a*²U¹¹ + . . . + 2 h k a* b* U¹²]. U11 U22 U33 U23 U13 U12 Au1 19(1)22(1) 17(1) 0(1) −1(1)  2(1) Au2 22(1) 21(1) 19(1) −1(1)  2(1) 5(1) P119(1) 20(1) 19(1) 0(1) 0(1) 1(1) P2 32(1) 27(1) 24(1) 2(1) 6(1) 12(1) N1 22(2) 21(2) 18(2) 1(2) 0(2) 4(2) N2 29(2) 36(3) 19(2) −4(2)  4(2)8(2) N3 25(2) 31(3) 29(3) 0(2) 0(2) 4(2) C1 17(2) 20(3) 16(2) −4(2) −2(2)  −2(2)  C2 17(2) 26(3) 20(3) −3(2)  1(2) −3(2)  C3 17(2) 27(3)31(3) 4(2) −2(2)  2(2) C9 34(3) 24(3) 22(3) −4(2)  11(2)  5(2) C10 41(3)62(4) 28(3) 3(3) 7(2) 10(3)  C11 43(4) 85(5) 35(4) 7(3) 16(3)  −2(3) C12 64(4) 64(4) 25(3) 9(3) 4(3) −13(3)  C13 47(3) 42(3) 25(3) 3(3) 2(2)−4(3)  C14 34(3) 31(3) 27(3) −1(2)  1(2) −1(2)  C15 40(3) 30(3) 43(4)−2(3)  0(3) 16(2)  C21 32(3) 45(3) 25(3) 9(3) 4(2) 13(2)  C22 60(4)68(5) 56(5) −14(4)  −11(3)  38(3)  C23 58(5) 100(6)  66(5) −2(5) −21(4)  43(4)  C24 29(3) 111(6)  32(4) 17(4)  −2(3)  8(4) C25 32(3)66(4) 47(4) 1(3) 3(3) 0(3) C26 26(3) 54(4) 46(4) 0(3) −1(3)  10(3)  C2722(2) 24(3) 17(3) 3(2) −1(2)  3(2) C33 19(2) 23(3) 15(2) −3(2)  −4(2) −4(2)  C34 24(3) 25(3) 23(3) 0(2) 0(2) 1(2) C35 32(3) 29(3) 25(3) 4(2)−2(2)  −5(2)  C36 27(3) 42(3) 30(3) 5(3) 2(2) −11(2)  C37 24(3) 36(3)34(3) −4(3)  3(2) −1(2)  C38 20(2) 26(3) 28(3) 2(2) −6(2)  −5(2)  C3920(2) 17(2) 23(3) −2(2)  1(2) 2(2) C40 20(2) 29(3) 20(3) 5(2) 0(2)−3(2)  C41 23(2) 41(3) 26(3) 0(3) −3(2)  −1(2)  C42 22(3) 33(3) 32(3)−3(3)  −6(2)  −6(2)  C43 37(3) 41(3) 36(3) 10(3)  −5(3)  −18(3)  C4439(3) 43(3) 26(3) 10(3)  −8(2)  −14(3)  C45 56(4) 47(4) 68(5) −2(4) 14(3)  −14(3)  C46 55(4) 41(4) 78(6) 15(4)  2(4) −7(3)  C47 45(4) 33(4)98(6) −4(4)  15(4)  9(3) C48 71(5) 68(5) 58(5) −13(4)  20(4)  −10(4) C49 59(4) 48(4) 65(5) 16(4)  −17(4)  5(3) C50 31(3) 45(4) 80(6) −17(4) 6(3) 5(3)

Computational Results for 3_(1,5).

TABLE 5 Optimized Cartesian coordinates of ground-state (singlet) for3_(1,5′). Atom x y z Au 3.13414 −0.50824 −0.12262 Au −3.1182 −0.536870.00241 P 5.42199 −0.15626 0.03395 P −5.4768 −0.14276 0.01235 N −0.61742−2.20306 −0.14505 N 1.09665 −0.87802 −0.21797 N 0.69437 −2.17095−0.22824 C 0.00288 −0.06645 −0.10413 C −1.10297 −0.92136 −0.05757 C0.09247 1.39864 −0.06948 C 0.95307 2.10346 −0.93354 C 1.03565 3.49634−0.88894 C 0.25346 4.22122 0.0136 C −0.61287 3.53672 0.87043 C −0.689922.14434 0.83298 C −5.91906 1.64342 0.01789 C −7.04495 2.15246 0.68227 C−7.33119 3.51873 0.63698 C −6.49876 4.38745 −0.07097 C −5.37225 3.88908−0.7297 C −5.07873 2.52632 −0.68116 C −6.32574 −0.84244 −1.46235 C−7.46026 −0.25348 −2.04098 C −8.06834 −0.84089 −3.15225 C −7.55017−2.01851 −3.69487 C −6.41668 −2.60632 −3.12886 C −5.80222 −2.01972−2.0222 C −6.35486 −0.86439 1.4596 C −7.67905 −1.3248 1.39691 C −8.29609−1.85073 2.53359 C −7.59838 −1.92331 3.74087 C −6.27752 −1.4749 3.80933C −5.65567 −0.95371 2.67445 C 5.88167 1.61643 −0.09362 C 7.11208 2.03318−0.62514 C 7.42779 3.39183 −0.68134 C 6.52032 4.34304 −0.2105 C 5.291253.93521 0.31247 C 4.96893 2.57899 0.36766 C 6.11015 −0.74971 1.62962 C7.18882 −0.11658 2.26506 C 7.69091 −0.62316 3.46548 C 7.12198 −1.761764.03903 C 6.04354 −2.39273 3.41448 C 5.53429 −1.88791 2.2182 C 6.37937−1.01757 −1.2754 C 7.66141 −1.54001 −1.04726 C 8.35813 −2.1665 −2.08254C 7.78291 −2.27718 −3.34966 C 6.50422 −1.76513 −3.58159 C 5.80208−1.1431 −2.54968 H 1.53634 1.55049 −1.6648 H 1.70148 4.01637 −1.57409 H0.31409 5.30632 0.04552 H −1.22478 4.08839 1.58033 H −1.34892 1.614251.51396 H −7.69305 1.48654 1.24408 H −8.2039 3.90273 1.15863 H −6.722175.45055 −0.10224 H −4.71282 4.56127 −1.2716 H −4.18823 2.14547 −1.17465H −7.86233 0.66931 −1.63301 H −8.9442 −0.37462 −3.5957 H −8.02297−2.47179 −4.56206 H −6.00094 −3.5152 −3.55474 H −4.90622 −2.4667 −1.5988H −8.22515 −1.28579 0.45903 H −9.32047 −2.20857 2.47283 H −8.07917−2.33751 4.62306 H −5.72478 −1.54246 4.74225 H −4.61968 −0.62825 2.72318H 7.81799 1.30128 −1.00644 H 8.38083 3.70563 −1.09838 H 6.76683 5.40019−0.25973 H 4.57413 4.67014 0.66661 H 4.00144 2.2693 0.75343 H 7.629250.77659 1.83217 H 8.52326 −0.12343 3.95347 H 7.51192 −2.15151 4.97534 H5.58885 −3.27151 3.86266 H 4.68199 −2.37033 1.74639 H 8.11183 −1.47102−0.06167 H 9.3483 −2.57272 −1.89495 H 8.3252 −2.76995 −4.15194 H 6.04589−1.86095 −4.56174 H 4.79843 −0.76625 −2.72856

Computational Results for 3_(1,4).

TABLE 6 Optimized Cartesian coordinates of ground-state (singlet) for3_(1,4). Atom x y z Au −1.82905 1.43078 −0.00219 Au 1.80779 0.57941−0.01463 P −3.64515 −0.01271 −0.02323 P 2.67095 −1.64619 0.03194 N0.66983 4.71031 0.03241 N −0.25841 2.76217 0.00994 N −0.488 4.101990.04587 C 1.08321 2.50081 −0.03233 C 1.66763 3.77544 −0.02028 C 3.076524.19284 −0.041 C 4.1148 3.32287 −0.42138 C 5.44403 3.74601 −0.42721 C5.77158 5.0539 −0.06228 C 4.74874 5.93288 0.30498 C 3.42113 5.510190.31626 C 4.50421 −1.69995 0.15092 C 5.27954 −2.69228 −0.46774 C 6.66901−2.68684 −0.3285 C 7.2948 −1.69385 0.42761 C 6.52977 −0.69946 1.04164 C5.14198 −0.69716 0.90056 C 2.06152 −2.65286 1.44506 C 2.82407 −3.673182.03472 C 2.30272 −4.41835 3.094 C 1.01878 −4.15238 3.5745 C 0.25681−3.13279 2.99973 C 0.77702 −2.38223 1.9448 C 2.25686 −2.62159 −1.47466 C1.99567 −3.9997 −1.44581 C 1.6991 −4.68572 −2.62579 C 1.6622 −4.00425−3.84419 C 1.9143 −2.62984 −3.88052 C 2.2033 −1.94001 −2.70249 C−3.76769 −1.04331 1.49495 C −4.24013 −2.36394 1.47533 C −4.337 −3.093532.6624 C −3.96546 −2.51205 3.87628 C −3.48846 −1.19838 3.90239 C−3.38389 −0.46813 2.71818 C −5.24227 0.88438 −0.13682 C −6.42828 0.374460.41409 C −7.62381 1.08287 0.28255 C −7.64473 2.30342 −0.39564 C−6.46652 2.82029 −0.93858 C −5.26797 2.1185 −0.80713 C −3.61676 −1.19425−1.42861 C −4.78912 −1.68816 −2.021 C −4.71137 −2.60508 −3.0709 C−3.46716 −3.0346 −3.53713 C −2.29585 −2.54062 −2.95837 C −2.36889−1.6201 −1.91269 H 3.86991 2.3092 −0.72856 H 6.22563 3.05225 −0.73031 H6.80712 5.38534 −0.07066 H 4.98703 6.95614 0.58689 H 2.62465 6.19050.59912 H 4.80264 −3.46168 −1.06769 H 7.26132 −3.45699 −0.8153 H 8.37651−1.68941 0.53057 H 7.01138 0.084 1.61971 H 4.55335 0.09176 1.3618 H3.82895 −3.87839 1.67751 H 2.90348 −5.20264 3.54667 H 0.61775 −4.731634.40193 H −0.73775 −2.91075 3.37638 H 0.19166 −1.5723 1.51737 H 2.01448−4.53749 −0.50279 H 1.4974 −5.753 −2.59102 H 1.43574 −4.54077 −4.76178 H1.88034 −2.0919 −4.82386 H 2.37954 −0.86767 −2.73202 H −4.52351 −2.827480.53526 H −4.70171 −4.11675 2.63611 H −4.04383 −3.08086 4.79886 H−3.19151 −0.74233 4.84261 H −2.99761 0.54778 2.74079 H −6.41783 −0.565790.95766 H −8.53651 0.68327 0.71609 H −8.57547 2.85579 −0.49148 H−6.47411 3.7767 −1.4533 H −4.34885 2.53606 −1.20994 H −5.76069 −1.34895−1.67444 H −5.62411 −2.97785 −3.52768 H −3.41093 −3.745 −4.3575 H−1.32411 −2.8597 −3.32432 H −1.45576 −1.21808 −1.48139

Synthesis of Substituted Homo-Bimetallic Complexes

Homo-bimetallic complexes with different R groups were substituted onthe acetylide group and used in the iClick reaction as shown in Scheme9, below.

Synthesis of 3-R(R═OMe, NO₂, F)

PPh₃-Au—N₃ ((1) 12.4 mg, 0.0248 mmol) and PPh₃-Au—C≡C—C₆H₄—R ((2-R)0.0248 mmol) were combined in a vial, to which 0.6 ml chloroform-d wasadded. The solution was transferred to an NMR tube, and reaction wasmonitored via NMR. Complete reaction was indicated by disappearance of¹H and ³¹P NMR resonances of the starting materials, Fluorine NMR wascarried out for the 3-F preparation. For 3-OMe, resonances attributableto the methyl protons on the methoxy group was easily monitored. All3-Rs display two slightly broadened signals in the ³¹P[{¹H} NMR spectrathat is very similar from compound to compound. The products, with theexception of 3-NO₂, were not isolated. 3-NO₂ was isolated by removingsolvent in vacuo, dissolving the residue in a minimal amount ofmethylene chloride, and precipitating the product as a bright yellowsolid, from pentane. Single crystals were grown by addition of pentaneto a methylene chloride solution of 3-NO₂. The molecular structure for3-NO₂ from x-ray data is shown in FIG. 11.

Synthesis of 3-Et

PPh₃-Au—N₃ (17.0 mg, 0.0339 mmol) and PPh₃-Au—C≡C-Et (17.4 mg, 0.0039mmol) were combined in a vial, to which 0.6 ml chloroform-d was added.The solution was transferred to an NMR tube, and the reaction wasmonitored via NMR. The reaction appeared to be complete within one hour,with the emergence of two resonances for the ethyl substituent (aquartet at 2.96 ppm, and a triplet at 1.42 ppm) and the disappearancesof the resonances attributable to the ethyl substituent in the startingmaterial (a quartet at 2.39 ppm and a triplet at 1.21 ppm). The product(3-Et) was isolated in 93% yield.

Synthesis of 3-C₄H₃S

PPh₃-Au—N₃ (63.0 mg, 0.111 mmol) and PPh₃-Au—C≡C—C₄H₃S (55.8 mg, 0.111mmol) were combined in a vial, to which 8 ml methylene chloride wasadded. The solution was stirred for 2 hours, and the solvent volume wasreduced in vacuo. about 5 ml hexane was added to the concentratedsolution to precipitate the colorless product.

TABLE 7 Selected notable NMR resonances for iClick reactions withsubstituted acetylenes. R H3 H4 H5 H6 R P1 P2 Ph—OMe — 8.3 (d, 6.85 (d,— OCH₃: 45.19 32.66 ³J_(HH) = ³J_(HH) = 3.82 (s) (s) (s) 8.21 Hz) 8.78Hz) Ph—NO₂ — 8.60 (d, 8.12 (d, — — 44.98 32.30 ³J_(HH) = ³J_(HH) = (s)(s) 8.5 Hz) 8.8 Hz) Ph—F — 8.34 (d, 8.32 (d, — F: −118.83 45.2 32.74³J_(HH) = ³J_(HH) = (s) (s) (s) 8.78 Hz) 8.78 Hz) C₄H₃S — 7.17 (s) 7.97(d, 7.90 (d, — 45.80 32.44 ³J_(HH) = ³J_(HH) = (s) (s) 4.53 Hz) 3.68 Hz)Et 2.96 (q, 1.42 (t, — — — 45.55 31.77 ³J_(HH) = ³J_(HH) = (s) (s) 7.64Hz) 7.64 Hz)

X-Ray Experimental for 3-NO₂:

X-Ray Intensity data were collected at 100K on a Bruker SMARTdiffractometer using MoKα radiation (λ=0.71073 Å) and an APEXII CCD areadetector.

Raw data frames were read by program SAINT¹ and integrated using 3Dprofiling algorithms. The resulting data were reduced to produce hklreflections and their intensities and estimated standard deviations. Thedata were corrected for Lorentz and polarization effects and numericalabsorption corrections were applied based on indexed and measured faces.

The structure was solved and refined in SHELXTL6.1, using full-matrixleast-squares refinement. The non-H atoms were refined with anisotropicthermal parameters and all of the H atoms were calculated in idealizedpositions and refined riding on their parent atoms. There are twochloroform solvent molecules in the asymmetric unit, one of which ispartially disordered where only two of the Cl atoms are disordered. Inthis case, atom C81 should also be disordered but it is to a lesserextent which did not allow for its resolution. In the final cycle ofrefinement, 10806 reflections (of which 9294 are observed with I>2σ(I))were used to refine 570 parameters and the resulting R₁, wR₂ and S(goodness of fit) were 2.13%, 4.96% and 0.981, respectively. Therefinement was carried out by minimizing the wR₂ function using F²rather than F values. R₁ is calculated to provide a reference to theconventional R value but its function is not minimized.

TABLE 8 Crystal data and structure refinement for 1-NO₂. Identificationcode apow6 Empirical formula C46 H36 Au2 Cl6 N4 O2 P2 Formula weight1345.36 Temperature 100(2) K Wavelength 0.71073 Å Crystal systemTriclinic Space group P ₁ Unit cell dimensions a = 13.1709(4) Å α =104.570(2)°. b = 13.9693(4) Å β = 113.005(1)°. c = 15.1962(4) Å γ =101.240(2)°. Volume 2352.00(12) Å³ Z 2 Density (calculated) 1.900 Mg/m³Absorption coefficient 6.682 mm⁻¹ F(000) 1292 Crystal size 0.35 × 0.06 ×0.05 mm³ Theta range for data collection 1.56 to 27.50°. Index ranges−17 ≦ h ≦ 17, −18 ≦ k ≦ 18, −19 ≦ l ≦ 19 Reflections collected 79139Independent reflections 10806 [R(int) = 0.0712] Completeness to theta =27.50° 100.0% Absorption correction Integration Max. and min.transmission 0.7142 and 0.2013 Refinement method Full-matrixleast-squares on F² Data/restraints/parameters 10806/0/570Goodness-of-fit on F² 0.981 Final R indices [I > 2sigma(I)] R1 = 0.0213,wR2 = 0.0496 [9294] R indices (all data) R1 = 0.0274, wR2 = 0.0515Largest diff. peak and hole 1.577 and −1.305 e.Å⁻³ R1 = Σ(||F_(o)| -|F_(c)||)/Σ|F_(o)| wR2 = [Σ[w(F_(o) ² - F_(c) ²)²]/Σ[w(F_(o) ²)²]]^(1/2)S = [Σ[w(F_(o) ² - F_(c) ²)²]/(n-p)]^(1/2) w = 1/[σ²(F_(o) ²) + (m*p)² +n*p], p = [max(F_(o) ², 0) + 2* Fc²]/3, m & n are constants.

Synthesis and characterization of 5-NO₂

To a 2-neck round bottom flask charged with a magnetic stirbar, wasadded chlorotriethylphosphine gold(I) (100 mg, 0.285 mmol), and1-ethynyl-4-nitrobenzene (50.4 mg, 0.342 mmol). The flask was evacuatedand then filled with argon and 5 mL of dry methanol was added viasyringe. 10 mL of a freshly prepared 0.262 M solution of sodiummethoxide in methanol (made from 60 mg (2.62 mmol) sodium metal in 10 mLdry methanol) was added via syringe. The suspension was allowed to stirunder argon for 16 h. The following workup was done with no precautionto exclude air and water. The solution volume was reduced in vacuo toapproximately 5 mL, at which time the yellow suspension was filteredthrough a glass fitted funnel, and the solid material was washed withcold methanol and pentane. The solid material was then taken up inchloroform, allowed to stir for 1 h and then all volatiles were removedin vacuo, and the residue triturated with pentane. The ³¹P{¹H} NMRreveals two resonances in the spectra of the initial solid material(39.96 and 37.92 ppm), which upon sitting in chloroform all productconverts to a single product (37.92 ppm)). 77% Yield (101 mg, 0.219mmol). ¹H NMR (500 MHz, CDCl₃): δ 8.10 (d, ³J_(HH)=8.6 Hz, 2H, H5), 7.56(d, ³J_(HH)=8.6 Hz, 2H, H4), 1.84 (dq, ²J_(PH)=7.6 Hz, ³J_(HH)=7.7 Hz,6H, H9), 1.22 (dt, ³J_(PH)=18.2 Hz, ³J_(HH)=7.7 Hz, 9H, H10). ¹³C NMRShifts (indirect detection through ¹H—¹³C gHMBC and ¹H—¹³C gHSQC (500MHz, CDCl₃)): δ 145.8 (C6), 132.8 (C4), 132.5 (C3), 123.4 (C5), 102.3(C2), 17.8 (C9), 8.9 (C10) (Note: C₁ is not observed). ³¹P{¹H} NMR(121.4 MHz, CDCl₃): δ 37.92 (s, P1). Anal. Calcd for C₁₄H₁₉AuNO₂: C,36.46; H, 4.15; N, 3.04. Found: C, 36.48; H, 4.13; N, 3.00.

Synthesis and Characterization of cis-6-pH

To a vial containing cis-(PPh₃)₂Pt(N₃)₂ (4-Ph) (15.5 mg, 0.0193 mmol)and PPh₃Au^(I)C≡CC₆H₄NO₂) (2-NO₂) (23.4 mg, 0.0386 mmol), was added 0.6ml C₆D₆. The suspension of the sparingly soluble platinum complex andthe soluble gold complex in benzene, was transferred to a sealable J.Young NMR tube, with an additional 0.2 ml of C₆D₆. The NMR tube wassealed and the mixture degased by a freeze-pump-thaw cycle. The reactionvessel was heated to 50° C. and maintained for 3.5 hours. All materialdissolved within 10 minutes, and within an additional 20 minutes, largeamounts of yellow crystalline solid had formed on the walls of the tube.After 3.5 hours the sample was slowly cooled to room temperature, whereadditional product crystallized overnight. A yellow crystalline solidwas isolated by decanting the supernatant and washing with pentane toprovide analytically pure cis-6-Ph in 90% yield (35.1 mg, 0.0174 mmol).NMR ¹H (300 MHz, CDCl₃): δ 8.04 (d, ³J_(HH)=8.7 Hz, 4H, H4), 7.95 (m,12H, H10), 7.83 (d, ³J_(HH)=9.0 Hz, 4H, H5), 7.60 (m, 18H, H11/H12),7.46 (t, ³J_(HH)=8.8 Hz, 12H, H54), 7.06 (t, ³J_(HH)=8.8 Hz, 6H, H56),6.73 (t, ³J_(HH)=7.2 Hz, 6H, H55). ¹³C NMR Shifts (indirect detectionthrough ¹H—¹³C gHMBC and ¹H—¹³C gHSQC (500 MHz, CDCl₃)): δ 151.5 (C2),144.4 (C3), 144.2 (C6), 134.9 (C10), 134.7 (C54), 131.6 (C9), 131.2(C12), 129.8 (C56), 129.3 (C11), 128.4 (C53), 127.5 (C55), 125.5 (C4),123.1 (C5). NMR ³¹P (121.4 MHz, CDCl₃): δ 43.53 (s, (P1)), 739 (s,w/satellites: ¹J_(Pt—P)=3095 Hz, (P3)). Anal. Calcd forC₈₈H₆₈Au₂N₈O₄P₄Pt: C, 52.47; H, 3.40; N, 5.56. Found: C, 52.38; H, 3.48;N, 5.71. The molecular structure for cis-6-Ph from x-ray data is shownin FIG. 7.

X-Ray Experimental for cis 6-pH:

X-Ray Intensity data were collected at 100K on a Bruker DUOdiffractometer using MoKα radiation (λ=0.71073 Å) and an APEXII CCD areadetector.

Raw data frames were read by program SAINT¹ and integrated using 3Dprofiling algorithms. The resulting data were reduced to produce hklreflections and their intensities and estimated standard deviations. Thedata were corrected for Lorentz and polarization effects and numericalabsorption corrections were applied based on indexed and measured faces.

The structure was solved and refined in SHELXTL6.1, using full-matrixleast-squares refinement. The non-H atoms were refined with anisotropicthermal parameters and all of the H atoms were calculated in idealizedpositions and refined riding on their parent atoms. The asymmetric unitconsists of four chemically equivalent but crystallographicallyindependent complexes, four and three fourth DCM solvent moleculesdisordered over 10 positions, and two and a half pentane solventmolecules disordered over five positions. Due to the presence of fourcomplexes in the asymmetric unit, a smaller unit cell was considered butthis introduced ligand disorders that are not present in the larger unitcell. Additionally, a check for higher or missed symmetry did notpresent any new possibilities. Pseudo-symmetry was explored but also didnot show any presence. Complex A shows no disorder while B has adisorder in the oxygen atoms of one nitro group. Complex C has onephosphorus atom and two of its phenyl rings disordered. A phenyl ring onthe neighboring phosphorus is also disordered. Complex D shows disorderin only one phenyl ring but with both nitro groups' oxygen atomsdisordered. One of the pentane molecules is disordered over seven carbonpositions. In each disorder case, two parts were dependently refined. Inthe final cycle of refinement, 77525 reflections (of which 36301 areobserved with I>2σ(I)) were used to refine 3958 parameters and theresulting R₁, wR₂ and S (goodness of fit) were 5.15%, 9.55% and 0.887,respectively. The refinement was carried out by minimizing the wR₂function using F² rather than F values. R₁ is calculated to provide areference to the conventional R value but its function is not minimized.

TABLE 9 Crystal data and structure refinement for cis-6-PhIdentification code apow11 Empirical formula C370.75 H311.50 Au8 Cl9.50N32 O16 P16 Pt4 Formula weight 8659.41 Temperature 100(2) K Wavelength0.71073 Å Crystal system Triclinic Space group P ₁ Unit cell dimensionsa = 27.823(3) Å α = 60.6370(10)°. b = 28.101(3) Å β = 61.9650(10)°. c =28.510(3) Å γ = 84.409(2)°. Volume 16889(3) Å³ Z 2 Density (calculated)1.703 Mg/m³ Absorption coefficient 5.327 mm⁻¹ F(000) 8467 Crystal size0.08 × 0.06 × 0.02 mm³ Theta range for data collection 0.84 to 27.50°.Index ranges −36 ≦ h ≦ 36, −36 ≦ k ≦ 36, −37 ≦ l ≦ 37 Reflectionscollected 236008 Independent reflections 77525 [R(int) = 0.1147]Completeness to theta = 27.50° 99.9% Absorption correction IntegrationMax. and min. transmission 0.8828 and 0.6814 Refinement methodFull-matrix least-squares on F² Data/restraints/parameters 77525/54/3958Goodness-of-fit on F² 0.877 Final R indices [I > 2sigma(I)] R1 = 0.0515,wR2 = 0.0955 [36301] R indices (all data) R1 = 0.1459, wR2 = 0.1142Largest diff. peak and hole 3.284 and −2.923 e.Å⁻³ R1 = Σ(||F_(o)| -|F_(c)||)/Σ|F_(o)| wR2 = [Σ[w(F_(o) ² - F_(c) ²)²]/Σ[w(F_(o) ²)²]]^(1/2)S = [Σ[w(F_(o) ² - F_(c) ²)²]/(n-p)]^(1/2) w = 1/[σ²(F_(o) ²) + (m*p)² +n*p], p = [max(F_(o) ²,0) + 2* F_(c) ²]/3, m & n are constants.

Synthesis and Characterization of cis-6-Et

To a vial containing cis-(PEt₃)₂Pt(N₃)₂ (4-Et) (14.5 mg, 0.0282 mmol)and PEt₃Au¹C≡CC₆H₄NO₂ (5-NO₂) (26.0 mg, 0.0564 mmol), was added 0.6 mlC₆D₆. The suspension of the sparingly soluble platinum complex andsoluble gold complex in benzene, was transferred to a sealable J. YoungNMR tube, with an additional 0.2 ml of C₆D₆. The NMR tube was sealed andthe mixture degassed using a freeze-pump-thaw cycle. The NMR tube washeated at 50° C. for 16 hours. Within the first 10 minutes all materialdissolved, and the solution turned yellow/green in color. After 16hours, the sample slowly cooled to room temperature and additionalproduct crystallized overnight. The solid material, a 60:23:17 mixtureof cis-6-Et, 8, and 7, was isolated by decanting the mother liquor, andwashing with pentane. Pentane addition into a chloroform solution of themixture selectively precipitates a mixture of cis-6-Et and 7 incrystalline form. Cis-6-Et was isolated from 7 by washing with coldbenzene. Yield of cis-6-Et 14.2 mg, 35% yield. NMR ¹H (300 MHz, CDCl₃):δ 8.31 (d, ³J_(HH)=8.95 Hz, 4H, H4), 7.83 (d, ³J_(HH)=8.95 Hz, 4H, 5H),1.77 (d, ³J_(HH)=8.95 Hz, 6H, H11D), 1.77 (d, ³J_(HH)=8.95 Hz, 6H,H11A), 1.73 (ddq, ²J_(HH)=13.2 Hz, ²J_(PH)=13.2 Hz, ³J_(HH)=7.7 Hz, 6H,H₄₁B), 1.29 (ddq, ²J_(HH)=13.6 Hz, ²J_(PH)=13.6 Hz, ³J_(HH)=7.6 Hz,61-1, H41A), 1.02 (dt, ³J_(PH)=8.0 Hz, ³J_(HH)=7.9 Hz, 18H, H42), 0.99(dt, ³J_(PH)=9.1 Hz, ³J_(HH)=8.4 Hz, 18H, H12). ¹³C NMR Shifts (indirectdetection through ¹H—¹³C gHMBC and ¹H—¹³C gHSQC (500 MHz, CDCl₃)): δ150.7 (C2), 144.3 (C6), 144.1 (C3), 124.8 (C4), 123.5 (C5), 17.4 (C11),14.9 (C41), 8.9 (C12), 8.5 (C42). NMR ³¹P (121.4 MHz, CDCl₃): δ 40.08(s, (P1)), 1.53 (s, w/satellites: ¹J_(Pt—P)=2974 Hz, (P3)). Anal. Calcdfor C₄₀H₆₈Au₂N₈O₄P₄Pt: C, 33.41; H, 4.77; N, 7.79. Found: C, 33.49; H,4.61; N, 7.90. The molecular structure for cis-6-Et from x-ray data isshown in FIG. 8.

X-Ray Experimental for cis-6-Et:

X-Ray Intensity data were collected at 100K on a Bruker DUOdiffractometer using MoKα radiation (λ=0.71073 Å) and an APEXII CCD areadetector.

Raw data frames were read by program SAINT¹ and integrated using 3Dprofiling algorithms. The resulting data were reduced to produce hklreflections and their intensities and estimated standard deviations. Thedata were corrected for Lorentz and polarization effects and numericalabsorption corrections were applied based on indexed and measured faces.

The structure was solved and refined in SHELXTL6.1, using full-matrixleast-squares refinement. The non-H atoms were refined with anisotropicthermal parameters and all of the H atoms were calculated in idealizedpositions and refined riding on their parent atoms. The asymmetric unitconsists of two platinum complexes and five benzene solvent molecules.The benzene molecules were disordered and could not be modeled properly,thus program SQUEEZE, a part of the PLATON package of crystallographicsoftware, was used to calculate the solvent disorder area and remove itscontribution to the overall intensity data. The C42, C34 and C36 unitswere disordered and refined in two parts with their site occupationfactors fixed (after refinements) at a ratio of 60/40. The N8′ nitrogroup did not refine properly thus it was constrained to maintain ageometry similar to the N4′ nitro group. In the final cycle ofrefinement, 136267 reflections (of which 19923 are observed withI>2σ(I)) were used to refine 1048 parameters and the resulting R₁, wR₂and S (goodness of fit) were 6.27%, 16.55% and 1.066, respectively. Therefinement was carried out by minimizing the wR₂ function using F²rather than F values. R₁ is calculated to provide a reference to theconventional R value but its function is not minimized. The highestresidual peaks are high although they do lie close to the gold centers.Models of the structure were refined with and without absorptioncorrections and the peaks persisted.

TABLE 10 Crystal data and structure refinement for cis-6-Et.Identification code tre05 Empirical formula C55 H83 Au2 N8 O4 P4 PtFormula weight 1633.20 Temperature 100(2) K Wavelength 0.71073 Å Crystalsystem Triclinic Space group P ₁ Unit cell dimensions a = 14.963(2) Å α= 70.137(3)°. b = 19.646(3) Å β = 86.619(3)°. c = 23.512(3) Å γ =76.690(3)°. Volume 6324.7(15) Å³ Z 4 Density (calculated) 1.715 Mg/m³Absorption coefficient 6.983 mm⁻¹ F(000) 3188 Crystal size 0.17 × 0.13 ×0.03 mm³ Theta range for data collection 1.13 to 27.50°. Index ranges−19 ≦ h ≦ 19, −25 ≦ k ≦ 25, −30 ≦ l ≦ 30 Reflections collected 136267Independent reflections 29055 [R(int) = 0.0678] Completeness to theta =27.50° 100.0% Absorption correction Integration Max. and mintransmission 0.8023 and 0.3920 Refinement method Full-matrixleast-squares on F² Data/restraints/parameters 29055/3/1048Goodness-of-fit on F² 1.066 Final R indices [I > 2sigma(I)] R1 = 0.0627,wR2 = 0.1655 [19923] R indices (all data) R1 = 0.0882, wR2 = 0.1737Largest diff. peak and hole 12.846 and −6.455 e.Å⁻³ R1 = Σ(||F_(o)| -|F_(c)||)/Σ|F_(o)| wR2 = [Σ[w(F_(o) ² - F_(c) ²)²]/Σ[w(F_(o) ²)²]]^(1/2)S = [Σ[w(F_(o) ² - F_(c) ²)²]/(n-p)]^(1/2) w = 1/[σ²(F_(o) ²) + (m*p)² +n*p], p = [max(F_(o) ², 0) + 2* Fc²]/3, m & n are constants.

Synthesis and Characterization of 8

To a vial containing cis-(PEt₃)₂Pt(N₃)₂ (4-Et) (14.5 mg, 0.0282 mmol)and PEt₃Au^(I)C≡CC₆H₄NO₂ (5-Et) (26.0 mg, 0.0564 mmol), was added 0.6 mlC₆D₆. The only sparingly soluble platinum complex suspension and solublegold complex in benzene was transferred to a sealable J. Young NMR tube,with an additional 0.2 ml of C₆D₆. The NMR tube was sealed and themixture degassed with a freeze-pump-thaw cycle. The NMR tube was heatedat 50° C. for 16 hours. Within the first 10 minutes all materialdissolved and the solution turned yellow/green in color. After 16 hours,the sample was immediately filtered to remove a mixture of crystallinesolid which consisted predominately of cis-6-Et and 7, with a very minoramount of 8. The volume of the benzene filtrate was reduced via slowevaporation by approximately 0.1 ml, and filtering was repeated. Thisfiltrate was reduced to approximately 0.2 ml by slow evaporation toyield additional crystalline material. This additional crystallinematerial was a 95:5 mixture of 8, and 7 by NMR that was isolated bydecanting the mother liquor, and washing the solid material withpentane. Pure 8 was not obtained via further fractionalrecrystallizations from the 5 molar percent impurity of 7. The yield of8 was 19.8% yield based on platinum. NMR ¹H (300 MHz, CDCl₃): δ 8.59 (d,³J_(HH)=8.2 Hz, 2H, (H4)), 8.17 (d, ³J_(HH)=8.2 Hz, 2H, (H5)), 8.12 (d,³J_(HH)=8.2 Hz, 2H, (H11)), 7.31 (d, ³J_(HH)=8.2 Hz, 2H, (H10)), 1.92(dq, ²J_(PH)=8.5 Hz, ³J_(HH)=7.9 Hz, (H15)), 1.82 (d, ³J_(HH)=8.2 Hz,(H13A)), 1.77 (ddq, ²J_(HH)=8.1 Hz, ²J_(PH)=8.1 Hz, ³J_(HH)=7.3 Hz,(H₁₃B)), 1.34 (dt, ³J_(PH)=17.6 Hz, ³J_(HH)=7.7 Hz, (H16)), 1.18 (dt,³J_(PH)=16.1 Hz, ³J_(HH)=8.1 Hz, (H14)). ¹³C NMR Shifts (indirectdetection through ¹H—¹³C gHMBC and ¹H—¹³C gHSQC (500 MHz, CDCl₃)): δ151.8 (C2), 144.9 (C6), 144.6 (C12), 143.6 (C3), 135.8 (C9), 131.1(C10), 125.1 (C4), 123.8 (C5), 123.7 (C11), 106.6 (C8), 17.9 (C15), 14.4(C13), 8.9 (C16), 8.1 (C14), (note: C1 and C7 are not observed). NMR ³¹P(121.4 MHz, CDCl₃): δ 40.0 (s, (P1)), 13.8 (s, w/satellites:¹J_(Pt—P)=2458.1 Hz, (P2)).

Synthesis and Characterization of 7

To a 2 ml chloroform solution of PEt₃Au^(I)C≡CC₆H₄NO₂ (5-NO₂) (60 mg,0.130 mmol) was added PEt₃Au^(I)N₃ (9) (46.5 mg, 0.130 mmol). Thisreaction mixture was stirred overnight, yielding a dark gold/orangesolution containing 7, which was isolated by removing the solventin-vacuo, and washing the residue with pentane. Analytically purematerial could be obtained by diffusion of pentane into a CH₂Cl₂solution of 7, which yields long, needle-like yellow crystals in 88%yield (93 mg, 0.0568 mmol). NMR ¹H (300 MHz, CDCl₃): δ 8.70 (d,³J_(HH)=8.9 Hz, 4H, H5), 8.14 (d, ³J_(HH)=8.69 Hz, 4H, H4), 1.51 (dq,²J_(PH)=7.6 Hz, ³J_(HH)=7.6 Hz, 12H, H17), 1.47 (dq, ²J_(PH)=7.5 Hz,³J_(HH)=7.5 Hz, 12H, H31), 1.10 (dt, ³J_(PH)=6.65 Hz, ³J_(HH)=7.71 Hz,18H, H32), 1.04 (dt, ³J_(PH)=6.65 Hz, ³J_(HH)=7.71 Hz, 18H, H18). ¹³CNMR Shifts (indirect detection through ¹H—¹³C gHMBC and ¹H—¹³C gHSQC(500 MHz, CDCl₃)): δ 151.1 (C2), 145.1 (C6), 143.7 (C3), 126.0 (C4),123.6 (C5), 17.2 (C31), 16.6 (C17), 8.5 (C32), 8.5 (C18). NMR ³¹P{¹H}(121.4 MHz, CDCl₃): δ 31.7 (s, P3/P4), 20.8 (s, P1/P2). Anal. Calcd forC₄₀H₆₈Au₄N₈O₄P₄: C, 29.35; H, 4.19; N, 6.85. Found: C, 29.42; H, 4.29;N, 6.98. The molecular structure for 7 from x-ray data is shown in FIG.9.

X-Ray Experimental for 7:

X-Ray Intensity data were collected at 100K on a Bruker DUOdiffractometer using MoKα radiation (λ=0.71073 Å) and an APEXII CCD areadetector.

Raw data frames were read by program SAINT¹ and integrated using 3Dprofiling algorithms. The resulting data were reduced to produce hklreflections and their intensities and estimated standard deviations. Thedata were corrected for Lorentz and polarization effects and numericalabsorption corrections were applied based on indexed and measured faces.

The structure was solved and refined in SHELXTL6.1, using full-matrixleast-squares refinement. The non-H atoms were refined with anisotropicthermal parameters and all of the H atoms were calculated in idealizedpositions and refined riding on their parent atoms. The asymmetric unitconsists of one Au₄ cluster and one diethyl ether solvent moleculedisordered over three positions. The solvent molecules were disorderedand could not be modeled properly, thus program SQUEEZE, a part of thePLATON package of crystallographic software, was used to calculate thesolvent disorder area and remove its contribution to the overallintensity data. All four triethylphosphine ligands are wholly disorderedand each was refined in two parts. Restrictions were applied using SADIto maintain equal P—C and C—C bonds in those ligands as well as usingEADP to maintain equivalent displacement parameters among similar atoms.Both nitro groups have their oxygen atoms disordered and each wasrefined in two parts. It is worth noting here that all possiblemerohedral twinning possibilities were explored but none fit. In thefinal cycle of refinement, 9435 reflections (of which 6179 are observedwith I>2σ(I)) were used to refine 483 parameters and the resulting R₁,wR₂ and S (goodness of fit) were 7.53%, 16.93% and 1.048, respectively.The refinement was carried out by minimizing the wR₂ function using F²rather than F values. R₁ is calculated to provide a reference to theconventional R value but its function is not minimized.

TABLE 11 Crystal data and structure refinement for 7. Identificationcode apow9 Empirical formula C44 H78 Au4 N8 O5 P4 Formula weight 1710.89Temperature 100(2) K Wavelength 0.71073 Å Crystal system RhombohedralSpace group R-3 Unit cell dimensions a = 46.159(2) Å α = 90°. b =46.159(2) Å β = 90°. c = 13.0682(6) Å γ = 120°. Volume 24113.7(18) Å³ Z18 Density (calculated) 2.121 Mg/m³ Absorption coefficient 11.086 mm⁻¹F(000) 14652 Crystal size 0.15 × 0.08 × 0.04 mm³ Theta range for datacollection 1.53 to 25.00°. Index ranges −51 ≦ h ≦ 51, −50 ≦ k ≦ 54, −15≦ l ≦ 15 Reflections collected 78284 Independent reflections 9435[R(int) = 0.1022] Completeness to theta = 25.00° 100.0% Absorptioncorrection Integration Max. and min. transmission 0.6976 and 0.2818Refinement method Full-matrix least-squares on F²Data/restraints/parameters 9435/255/483 Goodness-of-fit on F² 1.048Final R indices [I > 2sigma(I)] R1 = 0.0753, wR2 = 0.1693 [6179] Rindices (all data) R1 = 0.1169, wR2 = 0.1832 Largest diff. peak and hole2.746 and −1.392 e.Å⁻³ R1 = Σ(||F_(o)| - |F_(c)||)/Σ|F_(o)| wR2 =[Σ[w(F_(o) ² - F_(c) ²)²/Σ[w(F_(o) ²)²]]^(1/2) S = [Σ[w(F_(o) ² - F_(c)²)²]/(n-p)]^(1/2) w = 1/[σ²(F_(o) ²) + (m*p)² + n*p], p = [max(F_(o)²,0) + 2* F_(c) ²]/3, m & n are constants.

Synthesis and Characterization of [Au^(I)(C≡C-4-C₆H₄NO₂)]₂(μ-dppm) (10)

In a 100 ml Schlenk flask, 80 mg sodium metal (3.48 mmol) was added to20 mL of dry methanol under argon. After hydrogen gas evolution ceased,the sodium-methoxide in methanol solution was transferred via a syringeunder argon into a second Schlenk flask containing 200 mgAu₂(μ-dppm)₂Cl₂ (0.16 mmol) and 51 mg 2-ethynyl-4-nitrobenzene (0.34mmol). The pale yellow reaction mixture was stirred under argonovernight. The product was isolated as a pale-yellow powder byfiltration and washed with 5 mL of dry methanol and 10 mL of diethylether. After removing all volatiles in vacuo, complex 10 was obtained in92% yield (158 mg). ¹H NMR (500 MHz, CDCl₃) δ 7.98 (d, ³J_(HH)=8.3 Hz,4H, H5), 7.64 (dt, ³J_(PH)=8.2 Hz, ³J_(HH)=7.1 Hz, 8H, H9), 7.52 (d,³J_(HH)=8.3 Hz, 4H, H4), 7.46 (dd, ³J_(HH)=7.1 Hz, 4H, H11), 7.37 (dd,³J_(HH)=7.1 Hz, 8H, H10), 3.62 (dd, ³J_(PH)=10.3 Hz, 2H, H7). ¹³C{1H}NMR (126 MHz, CDCl₃) δ 145.7 (C6), 141.4 (C1), 133.4 (C9), 132.7 (C4),132.2 (C3, C11), 129.4 (C10), 129.0 (C8), 123.1 (C5) 103.5 (C2), 29.5(C7). ³¹P NMR (121.1 MHz, CDCl₃) δ 31.73 (s). Anal. Calcd. ForC₄₁H₃₀Au₂N₂O₄P₂: C, 46.00; H, 2.82; N, 2.62. Found: C, 46.05; H, 2.69;N, 2.63.

Synthesis and Characterization of 11

A sealable NMR tube was charged with 20 mg of 4-Et (0.039 mmol), 45 mgof 10 (0.042 mmol) and 1.5 mL CDCl₃. Yellow crystals formed uponstanding at room temperature for 2 days. Crystals were isolated bydecanting the supernatant and washing with 1 mL of chloroform and 5 mLof diethyl ether. The crystalline material was dried in vacuo to provide11 in 36% yield (22 mg). ¹H NMR (500 MHz, DMSO-d6) δ 8.39 (d, ³J_(HH)=9Hz, 4H, H14), 7.95 (d, ³J_(HH)=9 Hz, 4H, H15), 7.88 (m, 4H, H42), 7.66(dt, ³J_(PH)=6.9 Hz, ³J_(HH)=6.9 Hz, 4H, H52), 7.51 (m, 6H, 43-H, H44),7.37 (dd, ³J_(HH)=7.5 Hz, 2H, H54), 7.18 (dd, ³J_(HH)=7.6 Hz, 4H, H53),5.20 (dt, ³J_(PH)=³J_(HH)=13.4 Hz, 1H, H₁₉B), 3.70 (dt, ³J_(PH)=14.5 Hz,³J_(HH)=10.9 Hz, 1H, H19A), 1.62 (ddq, ²J_(PH)=15.3 Hz,³J_(HH)=²J_(HH)=7.7 Hz, 6H, H31), 1.51 (ddq, ²J_(PH)=15.4 Hz,³J_(HH)=²J_(HH)=7.6 Hz, 6H, H31), 0.98 (dt, ³J_(pH)=16.3 Hz, ³J_(HH)=7.5Hz, 18H, H32). ¹³C{1H} NMR (126 MHz, DMSO-d) δ 170.5 (C11), 149.6 (C12),144.5 (C16), 144.3 (C13), 134.4 (C52), 132.8 (C42), 132.2 (C54), 131.8(C44, C41), 130.4 (C51), 129.6 (C43), 129.3 (C53), 125.3 (C14), 124.1(C15), 23.3 (C19), 14.1 (C31), 8.3 (C32). ³¹P{¹H} NMR (121.1 MHz,DMSO-d6) δ 36.4 (s, P4), −1.6 (s, P2). Anal. Calcd. ForC₅₃H₆₀Au₂O₄N₈P₄Pt: C, 40.14; H, 3.87; N, 7.07. Found: C, 40.08; H, 3.74;N, 6.96. The molecular structure for 11 from x-ray data is shown in FIG.10.

X-Ray Experimental for 11:

X-Ray Intensity data were collected at 100K on a Bruker DUOdiffractometer using MoKα radiation (λ=0.71073 Å) and an APEXII CCD areadetector.

Raw data frames were read by program SAINT¹ and integrated using 3Dprofiling algorithms. The resulting data were reduced to produce hklreflections and their intensities and estimated standard deviations. Thedata were corrected for Lorentz and polarization effects and numericalabsorption corrections were applied based on indexed and measured faces.The structure was solved and refined in SHELXTL6.1, using full-matrixleast-squares refinement. The non-H atoms were refined with anisotropicthermal parameters and all of the H atoms were calculated in idealizedpositions and refined riding on their parent atoms. In complex A, N4Anitro groups are disordered and were refined in two parts. Both P1A andP2A are disordered and were refined in two parts with their respectiveethyl groups. In molecule B, only the N1B nitro groups are disordered.Partially disordered chloroform molecules as well as disordered pentanemolecules are also present in the structure. In all, the asymmetric unitconsists of two PtAu₂ complexes, and three and a third chloroformmolecules disordered over seven general and two symmetry positions.Attempts to remove the solvent area contributions to the overallintensity of the data failed because of the disordered partial solventmolecule's proximity to the complexes, thus good void calculations werenot possible. In the final cycle of refinement, 23814 reflections (ofwhich 13830 are observed with I>2σ(I)) were used to refine 1328parameters and the resulting R₁, wR₂ and S (goodness of fit) were 6.89%,18.71% and 1.365, respectively. The refinement was carried out byminimizing the wR₂ function using F² rather than F values. R₁ iscalculated to provide a reference to the conventional R value but itsfunction is not minimized.

TABLE 12 Crystal data and structure refinement for 11. Identificationcode xy04 Empirical formula C111.33 H114.80 Au4 Cl0.56 N16 O8 P8 Pt2Formula weight 3250.49 Temperature 100(2) K Wavelength 0.71073 Å Crystalsystem Rhombohedral Space group R-3 Unit cell dimensions a = 42.079(3) Åα = 90°. b = 42.079(3) Å β = 90°. c = 39.683(3) Å γ = 120°. Volume60851(8) Å³ Z 18 Density (calculated) 1.597 Mg/m³ Absorption coefficient6.543 mm⁻¹ F(000) 28084 Crystal size 0.14 × 0.13 × 0.09 mm³ Theta rangefor data collection 1.52 to 25.00°. Index ranges −49 ≦ h ≦ 24, 0 ≦ k ≦50, 0 ≦ l ≦ 47 Reflections collected 23814 Independent reflections 23814[R(int) = 0.0000] Completeness to theta = 25.00° 100.0% Absorptioncorrection Semi-empirical from equivalents Max. and min. transmission0.5844 and 0.4589 Refinement method Full-matrix least-squares on F²Data/restraints/parameters 23814/108/1328 Goodness-of-fit on F² 1.365Final R indices [I > 2sigma(I)] R1 = 0.0689, wR2 = 0.1871 [13830] Rindices (all data) R1 = 0.1422, wR2 = 0.2306 Largest diff. peak and hole3.934 and −1.762 e.Å⁻³ R1 = Σ(||F_(o)| - |F_(c)||)/Σ|F_(o)| wR2 =[Σ[w(F_(o) ² - F_(c) ²)²/Σ[w(F_(o) ²)²]]^(1/2) S = [Σ[w(F_(o) ² - F_(c)²)²]/(n-p)]^(1/2) w = 1/[σ₂(F_(o) ²) + (m*p)² + n*p], p = [max(F_(o)²,0) + 2* F_(c) ²]/3, m & n are constants.

Synthesis of Homo-Tetranuclear Complex 14

Synthesis of 13

To a 10 ml CHCl₃ solution of [PPh₃Au^(I)]₂[C≡C(C₄H₂S)₂C≡C] (44 mg, 0.039mmol) is added PPh₃Au^(I)N₃ (40 mg, 0.080 mmol). This reaction solutionis stirred for 1 h, at which point the solvent is removed in-vacuo. Theresidue is then extracted with 5 ml dichloromethane and filtered, andthe volume of the filtrate is reduced to ˜1 ml. Addition of 5 ml pentaneprecipitates the product as a brown-yellow solid in 65% (54 mg) yield.¹H NMR (300 MHz, CDCl₃) δ 7.46-7.53 (m, PPh₃-H), δ 7.02 (d, ³J_(HH)=3.78Hz, 2H, H2) δ 6.62 (d, ³J_(HH)=3.78 Hz, 21-I, H1). ³¹P NMR (121.1 MHz,CDCl₃) δ 44.52 (s, C—Au—P), δ 32.26 (bs, N—Au—P).

One of the indications of formation of IClick product is from phosphineNMR spectra. The phosphine signal of gold thiopheneacetylide compound isat δ 41.59 ppm and the gold azide phosphine signal is at δ 31.37 ppm.After the reaction, the corresponding starting material phosphinesignals disappeared and two new signals arise at δ 44.52 ppm and δ 32.26ppm. The other is from proton NMR. The H1 doublet chemical signal ofgold thiopheneacetylide compound is at 6.92 ppm while in the isolatedproduct, this doublet signal shifted to 6.62 ppm. And the IR spectragives direct evidence that cycloaddition reaction happened based on theazide stretch at 2149 cm⁻¹ disappeared for the final product.

It should be understood that the examples and embodiments describedherein are for illustrative purposes only and that various modificationsor changes in light thereof will be suggested to persons skilled in theart and are to be included within the spirit and purview of thisapplication.

We claim:
 1. A bimetallic substituted triazole compound, comprising oneor more 1,2,3-triazole units where at least one of the triazole units issubstituted by two metal ions in the 1 and 4 or 5 positions.
 2. Thecompound of claim 1, wherein the one or more triazole units substitutedwith two metal ions are further substituted independently with anorganic substituent in the 4 or 5 positions.
 3. The compound of claim 1,wherein the metal ions are independently Au, Ni, Pd, Pt, Ru, Fe, Mn, Rh,Ir, Cr, Cu, W or any other group 3-16 metal.
 4. The compound of claim 1,wherein one or more cluster complexes comprise one or both of the metalions of the bimetallic substituted triazole compound, wherein at leastone of the plurality of metal ions in the cluster complex is substitutedby at least one of the triazole units.
 5. The compound of claim 1,further comprising at least one ligand to at least one metal ion.
 6. Thecompound of claim 5, wherein the ligands are independently anyphosphorous based ligands, nitrogen based ligands, cyclopentadienylderivative, carbon monoxide, nitrosyl, alkyl, aryl, or pincer-typeligand.
 7. The compound of claim 1, comprising a plurality of triazoleunits wherein at least one metal is attached to two triazole units. 8.The compound of claim 7, wherein a multiplicity of triazole units areconnected by a multiplicity of metal ions as a linear polymeric chain ora polymeric network.
 9. The compound of claim 7, wherein the polymericnetwork comprises tetrahedral metal ions.
 10. The compound of claim 9,wherein the polymeric network comprises octahedral metal ions.
 11. Thecompound of claim 10, wherein the polymeric network is a two-dimensionalnetwork.
 12. The compound of claim 10, wherein the polymeric network isa three-dimensional network.
 13. A method for the preparation of thebimetallic substituted triazole compound of claim 1, comprising:providing at least one metal acetylide; providing at least one metalazide; and combining the metal acetylide and the metal azide; whereinthe azide and acetylide undergo cycloaddition to form a triazole ring,wherein the metal of the metal azide is a substituent at the 1 positionof the triazole ring and the metal of the metal acetylide is asubstituent at the 4 or 5 position of the triazole ring.
 14. The methodof claim 13, wherein the metal azides independently comprise a metal and1 to 6 azide groups.
 15. The method of claim 13, wherein the metalacetylides independently comprise a metal and 1 to 6 acetylide groups.16. The method of claim 13, wherein the acetylide groups areindependently unsubstituted or substituted with an organic group. 17.The method of claim 13, wherein the cycloaddition reaction is catalyzedby a copper (I) salt.